Hydrotreating catalyst as well as preparation method and application thereof

Abstract

The invention discloses a hydrotreating catalyst as well as a preparation method and application thereof. The method comprises the following steps: impregnating an alumina-based carrier in an impregnation liquid containing dopamine, a protective agent and hydrogenation active metal in a supersaturated manner, adjusting the pH value of the system to enable the dopamine to be self-polymerized on the surface of a pore channel of the alumina-based carrier, and then performing washing and heat treatment to obtain the hydrotreating catalyst. The hydrogenation catalyst prepared by the method provided by the invention has obviously improved desulfurization and denitrification activity and stability.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalysis, and in particular relates to a hydroprocessing catalyst and a preparation method and application thereof. Background Art

[0002] Regardless of the scenario and pace of future energy transitions, fossil fuels, represented by oil, will continue to be the primary energy source for decades to come. Therefore, hydrotreating catalysts used for oil purification will remain one of the most important catalysts on the market.

[0003] Due to its suitable mechanical strength, acidity, and pore structure, γ-Al2O3 has been widely used as a support or modified in the preparation of hydrorefining and hydrocracking catalysts. With increasingly stringent environmental regulations, the development of highly active hydroprocessing catalysts has become essential, and the performance and stability requirements have become increasingly complex. Improving the dispersion and loading of active components in catalysts is an effective approach to developing high-performance catalysts. The active metals on the surface of pure Al2O3 interact strongly with the support. Excessive interaction leads to strong interactions between the active metals and the support in the final catalyst, ultimately hindering the full sulfurization of the active metal oxides in the catalyst, resulting in suboptimal catalytic activity. Currently, the support can be modified by adding organic additives. The acidic functional groups can fully occupy the coordinatively unsaturated sites on the alumina surface, effectively preventing strong interactions between the metal and the support and increasing the number of active sites in the catalyst. Alternatively, a carbon coating can be applied to the alumina surface to achieve the same effect.

[0004] CN108067243B discloses a hydroprocessing catalyst, its preparation method, and application. The method comprises: modifying an alumina support with a nitrogen-containing organic acid solution or an aromatic carboxylic acid solution, drying the support at low temperature, then impregnating the support with an active component solution or an active metal and an additive, and then performing a high-temperature heat treatment to produce the hydroprocessing catalyst.

[0005] CN107442126B discloses a method for preparing a hydroprocessing catalyst. The method comprises preparing a carbon-modified alumina-based carrier, loading a hydrogenation-active metal component by an impregnation method, and drying to obtain the hydroprocessing catalyst. The preparation method of the carbon-modified alumina-based carrier comprises: sequentially or simultaneously introducing a water-soluble silicone oil, a soluble additive, and a carbon precursor into the alumina-based carrier, and heat-treating the carrier to obtain the carbon-modified alumina-based carrier.

[0006] CN110935464B discloses a method for preparing a carbon-containing hydrodemetallization catalyst. The method comprises: immersing alumina powder in an aqueous ammonium bicarbonate solution for sealed heat treatment; after the heat treatment, performing solid-liquid separation, drying the solid phase material; soaking the dried material in a carbon-containing precursor solution I; separating the solid and liquid after soaking; and drying the solid phase material to obtain modified rod-shaped alumina clusters; kneading the modified alumina clusters with pseudo-boehmite to form the formed product; drying the formed product, spraying it with a carbon-containing precursor solution II, drying it, and then sequentially carbonizing and microwave treating it under an inert atmosphere to obtain a carbon-containing alumina carrier; and loading the hydrogenation active component onto the carbon-containing alumina carrier to obtain a hydrodemetallization catalyst.

[0007] A drawback of the above-mentioned technology is that it can weaken the interaction between the active component and the support, which can lead to the active component easily flowing and agglomerating during the reaction, causing the active particles to continuously grow larger, reducing the dispersion of the active component in the catalyst, and thus continuously reducing the catalyst activity and significantly shortening its service life. Therefore, a hydroprocessing catalyst that balances "weakening the interaction between the metal and the support" and "preventing metal aggregation" is needed, which will greatly help improve its activity and stability. Summary of the Invention

[0008] In order to overcome the deficiencies in the prior art, the present invention provides a hydroprocessing catalyst and its preparation method and application. The hydroprocessing catalyst prepared by the method of the present invention has significantly improved desulfurization and denitrification activities and stability.

[0009] A first aspect of the present invention provides a method for preparing a hydroprocessing catalyst, comprising:

[0010] The alumina-based carrier is supersaturatedly immersed in an impregnation solution containing dopamine, a protective agent and a hydrogenation active metal, and the pH value of the system is adjusted to allow dopamine to self-polymerize on the pore surface of the alumina-based carrier. The catalyst is then washed and heat-treated to obtain a hydrogenation treatment catalyst.

[0011] In the method of the present invention, the alumina-based carrier can be a commercially available product or prepared according to conventional methods. The preparation method of the alumina-based carrier can be as follows: mixing and kneading aluminum hydroxide dry rubber powder, shaping it, and then drying and calcining it to form the alumina-based carrier. During the kneading process, conventional molding aids such as extrusion aids, binders, and peptizers can be added as needed. The alumina-based carrier can contain auxiliary components, such as at least one of silicon, phosphorus, titanium, zirconium, magnesium, etc., and the weight content of the auxiliary components in the carrier is less than 15%.

[0012] In the method of the present invention, the pore volume of the alumina-based carrier is 0.3-1.5 mL / g, and the specific surface area is 150-450 m 2 / g.

[0013] In the method of the present invention, the shape of the alumina-based carrier can be spherical, bar-shaped (cylindrical, butterfly-shaped, clover-shaped or four-leaf clover-shaped bar), etc. The shape of the carrier can be selected according to specific needs.

[0014] In the method of the present invention, the amount of dopamine added to the impregnation solution is 2 wt% to 40 wt%, preferably 4 wt% to 24 wt%, based on the mass of the alumina-based support. The solvent used in the solution containing dopamine, a protective agent, and a hydrogenation-active metal is at least one of water, methanol, or ethanol.

[0015] In the method of the present invention, the protective agent is a water-soluble olefin, preferably one or more of N-isopropylacrylamide sodium styrene sulfonate, sodium methallyl sulfonate, sodium allyl sulfonate, isopentenol, 3-methyl-3-butene-1-ol, allyl alcohol, etc., and more preferably one or more of N-isopropylacrylamide sodium styrene sulfonate, sodium methallyl sulfonate, and sodium allyl sulfonate.

[0016] In the method of the present invention, the amount of the protective agent added to the impregnation solution accounts for 0.5 wt% to 8 wt%, preferably 1 wt% to 5 wt%, of the alumina-based support.

[0017] In the method of the present invention, the hydrogenation-active metal includes Group VIII metals and Group VIB metals, wherein the Group VIII metal is preferably Ni and / or Co, and the Group VIB metal is preferably Mo. When preparing the impregnation solution, the molybdenum source that can be used is selected from one or more of molybdenum oxide, ammonium molybdate, ammonium tetrathiomolybdate, and ammonium paramolybdate; the nickel source is selected from one or more of nickel nitrate, basic nickel carbonate, nickel oxalate, nickel chloride, and nickel acetate; and the cobalt source is selected from one or more of cobalt nitrate, cobalt oxalate, basic cobalt carbonate, and cobalt chlorate.

[0018] In the method of the present invention, the amount of hydrogenation active metal added to the impregnation solution in terms of oxide is 12 wt% to 36 wt%, preferably 18 wt% to 32 wt%, based on the mass of the alumina-based support.

[0019] In the method of the present invention, the impregnation solution may further contain an auxiliary component. The auxiliary component may be selected from one or more of phosphorus, titanium, silicon, zinc, copper, zirconium, boron, fluorine, lanthanum, cerium, and vanadium. The auxiliary component is added to the impregnation solution in an amount of 0.5 wt% to 5 wt%, preferably 1 wt% to 3 wt%, based on the alumina-based support.

[0020] In the method of the present invention, the impregnation adopts supersaturated impregnation, wherein the volume of the impregnation liquid is 1.5 to 4.5 times, preferably 1.8 to 4.0 times, the saturated water absorption capacity of the alumina-based support.

[0021] In the method of the present invention, the immersion temperature is 10 to 80° C., preferably 30 to 60° C., and the immersion time is 1 to 30 hours, preferably 5 to 20 hours.

[0022] In the method of the present invention, the reagent for adjusting the pH value of the system is selected from one or more of ethylenediamine, ammonium carbonate, diethanolamine, triethanolamine, and Tris buffer.

[0023] In the method of the present invention, the pH value of the system is adjusted by immersing the carrier in the impregnation solution, shaking for 5-10 minutes, adding a pH adjusting agent to the system, and continuing to shake until the pH value of the system reaches 8 to 10. The pH value of the system after adding the pH adjusting agent is at least 0.5 higher than the pH value before adding the pH adjusting agent.

[0024] In the method of the present invention, after the carrier is impregnated with the impregnation liquid, the impregnation liquid is dried under the condition of not exceeding the decomposition temperature of the generated polydopamine. The drying temperature is generally 30°C to 200°C, preferably 50 to 120°C; the drying time is 0.5h to 20h, preferably 2 to 10h.

[0025] The hydroprocessing catalyst prepared by the method of the present invention employs an alumina-based support and contains Group VIII and Group VIB metals as hydrogenation-active metal components. The Group VIII metal is preferably Co and / or Ni, and the Group VIB metal is preferably Mo. The content of the Group VIII metal as oxide is 1 wt% to 10 wt%, preferably 2 wt% to 8 wt%, based on the mass of the alumina-based support. The content of the Group VIB metal as oxide is 10 wt% to 25 wt%, preferably 15 wt% to 23 wt%.

[0026] In the hydroprocessing catalyst prepared by the method of the present invention, the mass content of dopamine is 1% to 10%, preferably 2% to 6%, based on the mass of the alumina-based carrier.

[0027] The second aspect of the present invention provides a hydroprocessing catalyst prepared by the above method.

[0028] The third aspect of the present invention provides the use of the hydroprocessing catalyst prepared by the above method in the hydroprocessing of heavy distillate oil.

[0029] Furthermore, the distillation range of the heavy distillate oil raw material is 270-580° C., and the heavy distillate oil raw material is at least one of coker wax oil, vacuum gas oil, deasphalted oil, catalytic cracking cycle oil, shale oil and coal tar.

[0030] Furthermore, the hydrotreatment conditions are: reaction temperature of 350-430°C, preferably 360-390°C, reaction pressure of 4-16 MPa, preferably 6-14 MPa, and hydrogen-to-oil volume ratio of 600:1-1500:1, preferably 800:1-1000:1.

[0031] Furthermore, the purpose of the hydrotreatment is hydrodesulfurization and / or hydrodenitrogenation.

[0032] Compared with the prior art, the present invention has the following advantages:

[0033] The present invention first modifies the surface of an alumina-based carrier with dopamine and a protective agent, and then induces dopamine to self-polymerize on the carrier surface to form polydopamine by subsequently adjusting the pH value of the solution, effectively blocking the direct interaction between the hydrogenation active metal and the carrier, and forming a "network" structure on the carrier surface that is conducive to the efficient dispersion and anchoring of active components, thereby effectively "anchoring" the hydrogenation active metal and avoiding the flow and aggregation of the hydrogenation active metal; the protective agent introduced simultaneously with the dopamine can cover part of the acidic sites before the dopamine is polymerized, avoiding covering the active center when "anchoring" the metal, achieving effective matching of the acidic center and the hydrogenation center, and also preventing excessive polymerization of dopamine, ensuring the permeability of the catalyst pores, thereby improving the activity and stability of the catalyst. DETAILED DESCRIPTION

[0034] The present invention is described in detail below by way of examples, but the present invention is not limited to the following examples. In addition, % in the present invention is by weight unless otherwise specified.

[0035] In the present invention, the properties of the alumina carrier used in the examples and comparative examples are as follows: pore volume of 0.85 mL / g, specific surface area of ​​213 m 2 / g.

[0036] In the present invention, the preparation process of the impregnation solution is as follows: (1) preparing an aqueous solution of active metal components with basic nickel carbonate, molybdenum oxide, and phosphoric acid; (2) adding dopamine and a protective agent to the aqueous solution of the active metal components to obtain the impregnation solution.

[0037] Example 1

[0038] (1) 200 mL of an impregnation solution containing Mo, Ni, P, 4 g of dopamine, and 1 g of propylene alcohol was prepared. The active metal components (calculated as oxides) in the impregnation solution were 20 wt % Mo and 4 wt % Ni, based on the mass of the alumina-based support. The pH of the impregnation solution was 6.0.

[0039] (2) 100 g of alumina support was added to the impregnation solution, shaken for 5 min, and then ethylenediamine was added to adjust the solution pH to about 8.0. The solution was impregnated at 30° C. for 20 h, and then dried at 80° C. for 6 h to obtain the catalyst of the present invention, which was recorded as C1.

[0040] Example 2

[0041] (1) 300 mL of an impregnation solution containing Mo, Ni, P, 30 g of dopamine, and 5 g of sodium methyl allyl sulfonate was prepared. The active metal components (calculated as oxides) in the impregnation solution were 20 wt % Mo and 4 wt % Ni, based on the mass of the alumina-based support. The pH of the impregnation solution was 8.0.

[0042] (2) 100 g of alumina support was added to the impregnation solution, and diethanolamine was added after shaking for 5 minutes to adjust the solution pH to about 9. The solution was impregnated at 50° C. for 6 hours, and then dried at 120° C. for 3 hours to obtain the catalyst C2 of the present invention.

[0043] Example 3

[0044] (1) 400 mL of an impregnation solution containing Mo, Ni, P, 20 g of dopamine, and 4 g of sodium N-isopropylacrylamide-p-styrenesulfonate was prepared. The active metal components (calculated as oxides) in the impregnation solution were 20 wt % Mo and 4 wt % Ni, based on the mass of the alumina-based support. The pH of the impregnation solution was 7.5.

[0045] (2) 100 g of alumina support was added to the impregnation solution, shaken for 5 min, and then Tris buffer was added to adjust the solution pH to about 8.5. The solution was impregnated at 40° C. for 10 h, and then dried at 100° C. for 4 h to obtain the catalyst C3 of the present invention.

[0046] Example 4

[0047] (1) 250 mL of an impregnation solution containing Mo, Ni, P, 5 g of dopamine, and 3 g of prenol was prepared. The active metal components (calculated as oxides) in the impregnation solution were 20 wt % Mo and 4 wt % Ni, based on the mass of the alumina-based support. The pH of the impregnation solution was 7.0.

[0048] (2) 100 g of alumina support was added to the impregnation solution, shaken for 5 min, and then Tris buffer was added to adjust the solution pH to about 8.5. The solution was impregnated at 30° C. for 15 h, and then dried at 120° C. for 4 h to obtain the catalyst C4 of the present invention.

[0049] Example 5

[0050] (1) 300 mL of an impregnation solution containing Mo, Ni, P, 18 g of dopamine, and 5 g of sodium allyl sulfonate was prepared. The active metal components (calculated as oxides) in the impregnation solution were 20 wt % Mo and 4 wt % Ni, based on the mass of the alumina-based support. The pH of the impregnation solution was 8.0.

[0051] (2) 100 g of alumina support was added to the impregnation solution, shaken for 5 min, and then diethanolamine was added to adjust the solution pH to about 9.5. The solution was impregnated at 60° C. for 20 h, and then dried at 110° C. for 6 h to obtain the catalyst C5 of the present invention.

[0052] Comparative Example 1

[0053] (1) An aqueous solution of nickel nitrate, ammonium molybdate, and phosphoric acid was prepared as an impregnation solution. The active metal components (calculated as oxides) in the impregnation solution were 20 wt% Mo and 4 wt% Ni, based on the mass of the alumina-based support. Equal volumes of 100 g of the support were impregnated and dried at 120°C for 4 hours to obtain comparative catalyst DC1.

[0054] Comparative Example 2

[0055] (1) 300 mL of an impregnation solution containing Mo, Ni, P, and 18 g of dopamine was prepared. The active metal components (calculated as oxides) in the impregnation solution were 20 wt % Mo and 4 wt % Ni, based on the mass of the alumina-based support. The pH of the impregnation solution was 5.5.

[0056] (2) 100 g of alumina support was added to the impregnation solution, aged for 12 h in a water vapor-saturated atmosphere, and then vacuum dried at 40° C. for 2 h to obtain comparative catalyst DC2.

[0057] Comparative Example 3

[0058] (1) Prepare 100 mL of a solution containing 6 g of dopamine; place 100 g of a support in a beaker and slowly impregnate the support with the prepared solution. The impregnated support is then aged in a steam-saturated atmosphere for 12 hours and then oven-dried at 90°C for 20 hours to obtain a modified support.

[0059] (2) 100 mL of an impregnation solution containing Mo, Ni, and P was prepared. In the impregnation solution, the content of Mo as an active metal component (calculated as oxide) was 20 wt%, and the content of Ni was 4 wt%, based on the mass of the alumina-based support.

[0060] (3) The modified support was added to the impregnation solution, aged for 12 h in a water vapor-saturated atmosphere, and then vacuum dried at 40 °C for 2 h to obtain comparative catalyst DC3.

[0061] Comparative Example 4

[0062] Compared with Example 5, sodium allyl sulfonate was not added to prepare the impregnation solution, thereby obtaining comparative catalyst DC4.

[0063] Comparative Example 5

[0064] Compared with Example 5, without adding diethanolamine, the pH value was adjusted as follows:

[0065] (1) 300 mL of an impregnation solution containing Mo, Ni, P, 18 g of dopamine, and 5 g of sodium allyl sulfonate was prepared. The active metal components (calculated as oxides) in the impregnation solution were 20 wt % Mo and 4 wt % Ni, based on the mass of the alumina-based support. The pH of the impregnation solution was 8.0.

[0066] (2) 100 g of the alumina carrier was added to the impregnation solution, impregnated at 60° C. for 20 h, and then dried at 110° C. for 6 h to obtain a comparative catalyst DC5.

[0067] Example 6

[0068] The catalysts of the above examples and comparative examples were subjected to activity evaluation tests in a microreactor. Prior to evaluation, the hydroprocessing catalysts were treated with a cyclohexane solution of CS2 as the sulfiding solution. The cyclohexane solution had a CS2 concentration of 4 wt%, a sulfiding temperature of 330°C, a sulfiding pressure of 14.0 MPa, a sulfiding time of 6 hours, and a hydrogen to sulfiding solution volume ratio of 5:5.

[0069] The raw oil is catalytic diesel, the properties of which are shown in Table 1. The reaction hydrogen pressure is 14.0 MPa, the hydrogen-to-oil volume ratio is 1000:1, and the volume space velocity is 1.0 h -1 , the reaction temperature is 370℃.

[0070] Table 1 Properties of crude oil

[0071] <![CDATA[Density (20 °C) / g·cm -3 > 0.9267 Distillation range / ℃ IBP / 10% 276 / 364 30％ / 50％ 407 / 428 70％ / 90％ 473 / 529 95% / EBP 553 / 575 <![CDATA[S / μg·g -1 ]]> 29600 <![CDATA[N / μg·g -1 ]]> 1540

[0072] The hydrodesulfurization and denitrification activities of the catalyst are expressed as the hydrodesulfurization and denitrification activities relative to the reference agent (Comparative Example 1), and the relative hydrodesulfurization activity (RVA(S)) and relative hydrodenitrogenation activity (RVA(N)) of the catalyst are calculated according to formula (1) and formula (2), respectively:

[0073]

[0074]

[0075] Wherein, k(S) and k(N) represent the hydrodesulfurization and hydrodenitrogenation activities of the catalyst, respectively; k(DS) and k(DN) represent the hydrodesulfurization and hydrodenitrogenation activities of the reference agent (Comparative Example 1), respectively.

[0076] Wherein, Ssp is the sulfur content in the reaction product of the evaluation catalyst used; Ssf is the sulfur content in the reaction raw materials used; Sdp is the sulfur content in the reaction product of the reference agent; Nsp is the nitrogen content in the reaction product of the evaluation catalyst used; Nsf is the mass percentage of nitrogen in the reaction raw materials used; Ndp is the nitrogen content in the reaction product of the reference agent.

[0077] The hydrorefining evaluation results of the catalysts prepared in each embodiment and comparative example are shown in Table 2.

[0078] Table 2 Evaluation results

[0079]

[0080] As can be seen from Table 2, compared with the comparative example catalyst, the hydroprocessing catalyst prepared by the method of the present invention has higher hydrodesulfurization and denitrification activities, and is particularly suitable for the hydroprocessing process of heavy feedstocks.

Claims

1. A method for preparing a hydroprocessing catalyst, comprising: The alumina-based carrier is supersaturatedly immersed in an impregnation solution containing dopamine, a protective agent and a hydrogenation active metal, and the pH value of the system is adjusted to allow dopamine to self-polymerize on the pore surface of the alumina-based carrier. The catalyst is then washed and heat-treated to obtain a hydrogenation treatment catalyst.

2. The preparation method according to claim 1, characterized in that The properties of the alumina-based carrier are as follows: the pore volume of the alumina-based carrier is 0.3-1.5 mL / g, the specific surface area is 150-450 m 2 / g.

3. The preparation method according to claim 1, characterized in that In the impregnation solution, the amount of dopamine added is 2 wt% to 40 wt%, preferably 4 wt% to 24 wt%, based on the mass of the alumina-based support.

4. The preparation method according to claim 1, characterized in that The protective agent is a water-soluble olefin, preferably one or more of N-isopropylacrylamide sodium styrene sulfonate, sodium methallyl sulfonate, sodium allyl sulfonate, isopentenol, 3-methyl-3-butene-1-ol, and allyl alcohol, and more preferably one or more of N-isopropylacrylamide sodium styrene sulfonate, sodium methallyl sulfonate, and sodium allyl sulfonate.

5. The preparation method according to claim 1 or 4, characterized in that In the impregnation solution, the amount of the protective agent added is 0.5 wt% to 8 wt% of the alumina-based support, preferably 1 wt% to 5 wt%.

6. The preparation method according to claim 1, characterized in that The hydrogenation active metals include Group VIII metals and Group VIB metals, wherein the Group VIII metals are preferably Ni and / or Co, and the Group VIB metals are preferably Mo.

7. The preparation method according to claim 1, characterized in that In the impregnation solution, the amount of hydrogenation active metal added in terms of oxide is 12 wt% to 36 wt%, preferably 18 wt% to 32 wt%, based on the mass of the alumina-based support.

8. The preparation method according to claim 1, characterized in that The impregnation solution also contains auxiliary components, which are selected from one or more of phosphorus, titanium, silicon, zinc, copper, zirconium, boron, fluorine, lanthanum, cerium, and vanadium. The amount of the auxiliary added to the impregnation solution accounts for 0.5wt% to 5wt% of the alumina-based carrier, preferably 1wt% to 3wt%.

9. The preparation method according to any one of claims 1 to 8, characterized in that The impregnation adopts supersaturated impregnation, wherein the volume of the impregnation liquid is 1.5 to 4.5 times, preferably 1.8 to 4.0 times, the saturated water absorption capacity of the alumina-based support.

10. The preparation method according to claim 1, characterized in that The immersion temperature is 10-80° C., preferably 30-60° C., and the immersion time is 1-30 hours, preferably 5-20 hours.

11. The preparation method according to claim 1, characterized in that The reagent for adjusting the pH value of the system is selected from one or more of ethylenediamine, ammonium carbonate, diethanolamine, triethanolamine, and Tris buffer.

12. The preparation method according to claim 1 or 11, characterized in that: The pH value of the system is adjusted by immersing the carrier in the impregnation solution, shaking for 5-10 minutes, adding a system pH adjusting agent and continuing to shake until the pH value of the system reaches 8-10; preferably, the pH value of the system after adding the pH adjusting agent is at least 0.5 higher than that before adding the pH adjusting agent.

13. The preparation method according to claim 1, characterized in that After the carrier is impregnated with the impregnation solution, it is dried under conditions not exceeding the decomposition temperature of the generated polydopamine; Preferably, the drying temperature is 30° C. to 200° C., preferably 50° C. to 120° C.; and the drying time is 0.5 h to 20 h, preferably 2 h to 10 h.

14. The preparation method according to claim 1, characterized in that The hydroprocessing catalyst prepared by the method has a content of Group VIII metal in the form of oxide of 1 wt% to 10 wt%, preferably 2 wt% to 8 wt%, based on the mass of the alumina-based carrier; and a content of Group VIB metal in the form of oxide of 10 wt% to 25 wt%, preferably 15 wt% to 23 wt%.

15. The preparation method according to claim 1, characterized in that In the hydroprocessing catalyst prepared by the method, the mass content of dopamine is 1% to 10%, preferably 2% to 6%, based on the mass of the alumina-based carrier.

16. A hydroprocessing catalyst prepared by the method according to any one of claims 1 to 15.

17. Use of the hydroprocessing catalyst according to claim 16 in the hydroprocessing of heavy distillate oil, characterized in that: The purpose of the hydrotreatment is hydrodesulfurization and / or hydrodenitrogenation.

18. The use according to claim 16, characterized in that The distillation range of the heavy distillate oil raw material is 270-580° C., and the heavy distillate oil raw material is at least one of coker wax oil, vacuum gas oil, deasphalted oil, catalytic cracking cycle oil, shale oil and coal tar; Preferably, the hydrotreatment conditions are: reaction temperature of 350-430°C, preferably 360-390°C, reaction pressure of 4-16 MPa, preferably 6-14 MPa, and hydrogen-to-oil volume ratio of 600:1-1500:1, preferably 800:1-1000:1.

Images